Umicore

The present disclosure concerns a process for the recovery of valuable metals from polymetallic nodules. A two-stage process using SO 2 in an acidic aqueous media is disclosed. In a first step, performed in mildly acidic conditions, Mn, Ni, and Co are dissolved; in a second, more acidic step, Cu is dissolved. Under these conditions, the leachate of the first step contains most of the Mn, Ni, and Co, while being nearly Cu-free. The Ni and Co are precipitated as sulfides; the Mn can be recovered as sulfate by crystallization. Cu, which is leached in the second step, is secretively precipitated, also as sulfide.

A method for preparing a N(M)C-based positive electrode materials according to the present invention comprises the following steps: —Precipitation of a metal (at least Ni— and Co—, preferably comprising Mn—) bearing precursor (MBP), —Fractionation of the MBP in a first (A) fraction and at least one second (B) fraction, —Lithiation of each of the first and second fraction, wherein the A fraction is converted into a first polycrystalline lithium transition metal oxide-based powder and the B fraction(s) is(are) converted into a second lithium transition metal oxide-based powder and, and —Mixing the first and second monolithic lithium transition metal oxide-based powder to obtain the N(M)C-based positive electrode material.

A cobalt oxide precursor powder for use in preparing a positive electrode active material and methods of production thereof are described. The precursor powder comprises particles has a Fd-3m structure and a formula Co 1-y A y O x , wherein 1<x≤4/3, 0≤y≤0.05, wherein A comprises at least one element from the group consisting of Ni, Mn, Al, Mg, Ti, and Zr. The particles have a D50≥15 μm and a compressive strength at least 100 MPa and at most 170 MPa.

The present disclosure concerns a process for the concentration of lithium in metallurgical fumes. The process comprises the steps of: —providing a metallurgical molten bath furnace; —preparing a metallurgical charge comprising lithium-bearing material, transition metals, and fluxing agents; —smelting the metallurgical charge and fluxing agents in reducing conditions in said furnace, thereby obtaining a molten bath with an alloy and a slag phase; and, —optionally separating the alloy and the slag phase; characterized in that a major part of the lithium is fumed as LiCl from the molten slag, by addition of alkali or earth alkali chloride to the process. Using a single smelting step, valuable transition metals such as cobalt and nickel also present in the charge are collected in an alloy phase, while the lithium reports to the fumes. The lithium in the fumes is available in concentrated form, suitable for subsequent hydrometallurgical processing.

A rechargeable lithium ion battery including: a positive electrode including coated particles, wherein each particle includes a core and a coating disposed thereon, wherein the core consists of Li, M, and O, and the coating includes Li, M, O, and AI2O3; wherein: M is (Ni z (Ni 1/2 Mn 1/2 ) y Co x ) 1−k A k ; 0.15≤z≤0.50; 0.17≤x≤0.30; 0.35≤y≤0.75; 0<k<0.1; x+y+z=1; and A includes Al and optionally at least one additional metal dopant selected from Mg, Zr, W, Ti, Cr, V, Nb, B, and Ca, and combinations thereof; and wherein the Li and M are present in the core in a molar ratio of Li to M of at least 0.95 and no greater than 1.10; a negative electrode; and a nonaqueous liquid electrolyte including: a lithium salt; a nonaqueous solvent; and an additive mixture including: prop-1-ene-1,3-sultone; at least one compound selected from tris(trimethylsilyl)phosphite, tris(trimethylsilyl)phosphate, tri-allyl phosphate, and combinations thereof; and at least one compound selected from methylene methanedisulfonate, 1,3,2-dioxathiolane-2,2-dioxide, and combinations thereof.

A lithium metal oxide powder for a cathode material in a rechargeable battery comprises a core and a surface layer. The surface layer is delimited by an outer and an inner interface. The inner interface is in contact with the core. The cathode material has a layered crystal structure comprising the elements Li, M, and oxygen. M has the formula M=(Ni z (Ni 1/2 Mn 1/2 ) y Co x ) 1-k A k , with 0.15≤x≤0.30, 0.20≤z≤0.55, x+y+z=1 and 0<k≤0.1. The Li content is stoichiometrically controlled with a molar ratio 0.95≤Li:M≤1.10. A is at least one dopant and comprises Al. The core at the inner interface has an Al content of 0.3-3 mol %. The surface layer comprises an intimate mixture of Ni, Co, Mn, LiF and Al 2 O 3 determined by XPS. The surface layer has a Mn content that decreases from the Mn content at the inner interface to less than 50% of the Mn content at the outer interface.

A precursor compound for manufacturing a lithium transition metal based oxide powder usable as an active positive electrode material in lithium-ion batteries, the precursor being either one of a metal-bearing M′-hydroxide, -oxyhydroxide or -carbonate, with M′=Ni 1-x-y-z Mn x CO y A z with x>0, y>0, 0.70≤1-x-y-z≤0.95 and 0≤z<0.1, the precursor comprising having a core comprising a metal-bearing compound M′ c and a shell comprising a metal-bearing compound M′ s , wherein M′ c =Ni 1-xc-yc-zc Mn xc CO yc A zc with 0<xc≤0.2, 0<yc≤0.2, 0≤zc<0.1 and 0.75≤1-x-y-z≤0.95, and M′ s =Ni 1-xs-ys-zs Mn xs CO ys A zs with 0<xs≤0.25, 0.75<ys≤0.95, 0≤zs<0.1 and 0≤ 1-xs-ys-zs ≤0.10.

A method for manufacturing a cobalt based hydroxide carbonate compound having a malachite-rosasite mineral structure, comprising the steps of: providing an first aqueous solution comprising a source of Co, providing a second aqueous solution comprising Na 2 CO 3 , mixing both solutions in a precipitation reactor at a temperature above 70° C., thereby precipitating a cobalt based hydroxide carbonate compound whilst evacuating from the reactor any CO 2 formed by the precipitation reaction, wherein the residence time of the compound in the reactor is between 1 and 4 hours, and recovering the cobalt based hydroxide carbonate compound. The cobalt based hydroxide carbonate compound is used as a precursor of a lithium cobalt based oxide usable as an active positive electrode material in lithium ion batteries.

A process is divulged for the recovery of lithium from metallurgic slags comprising the steps of roasting spodumene to convert it from the alpha to the beta variant; reacting the beta variant with sulfuric acid, using a stoichiometric excess of acid; repulping the reaction product with water, forming an acidic slurry; neutralizing the acidic slurry to a pH between 5 and 7, by addition of at least one neutralizing agent; filtrating the neutralized slurry, thereby obtaining a lithium bearing solution and a residue; characterized that, in either one or both of the steps of repulping and neutralizing the acidic slurry, lithium-bearing metallurgic slag is added as neutralization agent. The lithium-bearing metallurgic slag is used to substitute at least part of the classic neutralizing agent. The lithium in the slag is released, and added to the lithium liberated from the spodumene.

A secondary Li-ion battery comprising a casing comprising as battery parts: a positive electrode comprising a powderous positive electrode active material, a negative electrode, a separator, and an electrolyte, wherein the casing is provided with means for maintaining the exterior form of the casing, and wherein the positive electrode active material has the general formula Li 1+a (Ni x Co y M z ) 1−a O 2 , wherein M=M′ 1−b A b , M′ being either one or both of Al and Mg, and A being a dopant with b≤0.10, and wherein −0.03≤a≤0.03, 0.80≤×≤0.95, 0.05≤y≤0.20, z≤0.10, with x+y+z=1, and wherein the positive electrode active material has a crystallite size ≤43 nm as determined by the Sherrer equation based on the peak of the (104) plane obtained from the X-ray diffraction pattern using a Cu Kα radiation source, and wherein the positive electrode active material further comprises between 0.4 and 0.6 wt % LiOH.